Derivatives of phenyl-phenyl esters



Patented Dec. 27, 1938 UNITED STATES- OFFICE 12,141,172 DERIVATIVES or PHENYL-PHENYLESTERS Walter G. Christiansen, Glen Ridge, N, .L, and I Sidney E. Harris, Lynbrook, N. 2., assignors to E. B. Squibb & Sons, New 'York,

. poration of New York No Drawing. Original application September '7,

1933, Serial No. plication July 2,

'7 Claims.

; an alkyl or a halogen.

EXAMPLES 2-phenyZ-4-n-propylephenyl acetate 4.3 g. 2-hydroxy 5-n-propy1 diphenyl and cc. acetic anhydride are refluxed for half an hour and then poured into water the precipitated oil is extracted with ether; the extract is washed with sodiumcarbonate solution and dried with calcium chloride; and after removing the ether, the desired compound is distilled in vacuo, boiling at 168-17575 mm;

MonochZoro-3-phenyl phenyl benzoate 31 g. monochloro 3-hydroxy diphenyl, 24 g. benzoyl chloride, 33 cc. 35% sodium hydroxide, and 100 cc. water are shaken until the benzoyl chloride odor disappears; the thick oily product is extracted with ether; the extract is washed with dilute sodium hydroxide and water and dried with calcium chloride; and, the ether being distilled off, the desired compound remains as a viscous oil.

2-chlo1o-4-phem1l-phenyl benzoate 51 g. 3-ohloro 4-hydroxy diphenyl, 43 g. benzoyl chloride, 57 cc. 35% sodium hydroxide, and 150 cc. water, being interacted as in the precedingtwo examples, the desired compound is obtained, on recrystallization from hot alcohol, in the form of crystals melting at 110l1l (corrected).

Z-phenyl-si-bromo-phenyl acetate g. Z-hydroxy 5-bromo diphenyl is heated with 30 cc. acetic anhydride under a reflux condenser for one hour; the product is poured into water and stirred vigorously to decompose the excess of acetic anhydride; and the residual oil, on being washed several times with sodium carbonate solution and then with water, solidifies 688,496. Divided and this ap- 1936, Serial No. 88,590,

into hard white crystals of the desired compound, which on recrystallization from diluted alcohol melt at 66-67".

z-phenyl-fi-chloro-phenyl benzoate 50 g.; Z-hydroxy 3-ch1orodiphenyl is dissolved in 250 cc. 10% sodium hydroxide; 50 cc. benzoyl chloride is added; the mixture is vigorously shaken until all the benzoyl chloride has undergone reaction; the, crystalline mass formed is washed successively with cold dilute, sodium hydroxide solution andwater; and recrystallization from, petroleum ether yields the desired compound as a white crystalline solid melting at, 86-87 (corrected).

z-phenyl--chloro-phenyl benzoate.

40 g. 2-hydroxy 5-chloro diphenyl is dissolved in 250' cc. dry toluene; 30 g. benzoyl chloride is added; the mixture is refluxed until the evolution of hydrogen chloride ceases, is allowed to cool, is washed several times with cold 5% sodium hydroxide and then with water, and is dried with calcium chloride; the toluene is removed under reduced pressure; and recrystallization of the residue from methyl alcohol yields the desired compound as fine white needles melting at 885 (corrected) Monobromo-3-phenyl-phenyl benzoute 5 g. monobromo 3-hydroxy diphenyl is dissolved in 50 cc. 10% sodium hydroxide solution; 5 cc. benzoyl chloride is added; the mixture is vigorously shaken until the odor of benzoyl chloride has disappeared; the oily precipitate formed is extracted with ether; the ether solution is washed thoroughly with 5% sodium hydroxide solution and water and dried with calcium chloride; and on distillating oii the ether the desired compound remains as a thick oil.

2-phenyZ-4-n-propyZ-phenyl benzoate 42 g. Z-hydroxy 5-n-propyl diphenyl is dissolved in 250 cc. dry toluene; 26.5 g. benzoyl chloride is added; the mixture is refluxed until the evolutionof hydrogen chloride ceases, is allowed to cool, is washed with cold 5% sodium hydroxide and then with water, and is dried with calcium chloride; the toluene is removed by distillation under reduced pressure; and by recrystallization from petroleum ether the desired compound is obtained as white needles melting at 96 (corrected).

Z-phenfiuZ-G-chloro-phenyl cinnamate 40 g. 2-hydroxy 3-chloro-diphenyl and 30 g.

cinnamic acid are dissolved in 250 cc. toluene; 15 cc. phosphorus trichloride is added; the mixture is refluxed until the evolution of hydrogen chloride ceases; the toluene solution is decanted from the precipitated phosphorous acid; the toluene is completely removed by distillation under reduced pressure; the residue is dissolved in a suitable solvent such as water and dried with calcium chloride; the ether is distilled 01f; and the residue, on recrystallization from petroleum ether or from dilute alco-* hol, yields the desired compound as white needles melting at 74.5-'75 (corrected).

Z-phenyl-4-n-propyZ-phenyl cinnamate 40 g. 2-hydroxy 5-n-propyl diphenyl and g.

clnnamic acid are dissolved in 250 cc. dry toluene;

50 cc. phosphorus oxychloride is added; the mixture is refluxed until the evolution of hydrogen chloride ceases, is allowed to cool, and is washed with dilute sodium hydroxide solution and water and dried'with calcium chloride; the toluene is distilled off under reduced pressure; the residue, on being recrystallized from petroleum ether, yields the desired compound as fine matted white needles melting at 725 (corrected).

Z-PhenyZ-6-chloro-phenyl salicylate 41 g. Z-hydroxy S-chloro diphenyl is dissolved in 250 cc. dry toluene; 25 g. salicylic acid is dissolved in the solution; 15.5.g. phosphorus oxychloride is added; the mixture is refluxed until the evolution of hydrogen chloride ceases; the

' toluene solution is decanted from the precipitated ether; the solution is washed with 5% sodium hydroxide solution and We claim: 1. Compounds having the general formula CoHa XOCuHa wherein X represents a carboxylic acyl and Y represents a member'of the group consisting of alkyl and halogen.

2. Compounds having the general formula wherein X represents a carboxylic acyl and Y represents a member of the group consisting of alkyl and halogen.

3. Compounds having the general formula X 0 Qhalogen wherein 'X represents a carboxylic acyl.

4. Compounds having the general formula Cu s wherein X represents an acyl of the group consisting of .acetyl, benzoyl, cinnamoyl, and salicylyl and Y represents a member of the group consisting'of alkyl and halogen. 1

5. 2-phenyl-4-bromo phenyl acetate.

6. 2-phenyl-l-n-propyl-phenyl benzoate.

7. 2-phenyl-6-chloro-phenyl salicylate.

WALTER G. CHRISTIANSENV SIDNEY E. HARRIS. 

